Nature of Highly Active Electrocatalytic Sites for the Hydrogen Evolution Reaction at Pt Electrodes in Acidic Media

The hydrogen evolution reaction (HER) is one of the two processes in electrolytic water splitting. Known for more than two centuries, the HER still receives great attention in fundamental and applied science in view of its apparent simplicity (only two electrons are transferred), fast kinetics in acidic media, and promising technological applications in electrolyzers. However, the exact nature of active catalytic sites for this reaction is often uncertain, especially at nonuniform metal electrodes. Identification of such centers is important, as the HER will probably be central in future energy provision schemes, and it is simultaneously a convenient model reaction to study structure-composition-activity relations in catalysis. In this work, using simple coordination-activity considerations, we outline the location and geometric configuration of the active sites at various model Pt single-crystal electrodes. We show that when the coordination of such surface sites is optimized and their density at the surface is maximized, the experimental-specific HER activities are among the highest reported in the literature for pure platinum with a well-defined surface structure under similar conditions.